WO2017085268A1 - Structure de laque multicouche présentant un catalyseur thermolatent - Google Patents

Structure de laque multicouche présentant un catalyseur thermolatent Download PDF

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Publication number
WO2017085268A1
WO2017085268A1 PCT/EP2016/078160 EP2016078160W WO2017085268A1 WO 2017085268 A1 WO2017085268 A1 WO 2017085268A1 EP 2016078160 W EP2016078160 W EP 2016078160W WO 2017085268 A1 WO2017085268 A1 WO 2017085268A1
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WO
WIPO (PCT)
Prior art keywords
basecoat
clearcoat
polyisocyanate
substrate
film
Prior art date
Application number
PCT/EP2016/078160
Other languages
German (de)
English (en)
Inventor
Jan Weikard
Tanja Hebestreit
Frank Richter
Original Assignee
Covestro Deutschland Ag
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Filing date
Publication date
Application filed by Covestro Deutschland Ag filed Critical Covestro Deutschland Ag
Priority to US15/776,109 priority Critical patent/US20180320019A1/en
Priority to CN201680079625.9A priority patent/CN108472684B/zh
Priority to EP16802006.3A priority patent/EP3377235A1/fr
Publication of WO2017085268A1 publication Critical patent/WO2017085268A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/53—Base coat plus clear coat type
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/53—Base coat plus clear coat type
    • B05D7/532—Base coat plus clear coat type the two layers being cured or baked together, i.e. wet on wet
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/242—Catalysts containing metal compounds of tin organometallic compounds containing tin-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/002—Priming paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/06—Coating on the layer surface on metal layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2375/00—Polyureas; Polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2150/00—Compositions for coatings
    • C08G2150/90—Compositions for anticorrosive coatings

Definitions

  • the present invention relates to a process for producing a multi-layered paint construction, e.g. for automobile bodies, which at low curing temperatures leads to multilayer coating structures with a good intercoat adhesion, the multi-layered paint system obtainable therefrom and the use of the multilayer coating system for coating
  • the paint When painting high-quality goods such as Automobiles, the paint is usually applied in several layers.
  • a primer is first applied, which should improve the adhesion between the substrate and the subsequent layers depending on the substrate and also serves to protect the substrate from corrosion, if this is susceptible to corrosion.
  • the primer provides for an improvement of the surface texture by covering possibly existing roughness and structure of the substrate.
  • a filler On the primer, especially in metal substrates, often a filler is applied, whose task is the further improvement of the surface texture and the improvement of stone chip susceptibility.
  • On the filler usually one or more color and / or effect layers are applied, which are referred to as basecoat.
  • a high-crosslinked clearcoat is usually applied, which provides the desired glossy appearance and protects the paint system against environmental influences.
  • the basecoat is chemically crosslinked in addition to a physical drying.
  • derivatives of melamine are used as cost-effective crosslinkers. However, these must be cured at temperatures well above 120 ° C together with the clearcoat.
  • WO 2014/009221 and WO 2014/009220 describe polyisocyanate crosslinkers which are said to have improved diffusion into the basecoat. This is accomplished by incorporating hydrophilic groups into the crosslinkers or using certain low viscosity crosslinkers. However, the resulting improved diffusion effect is not strong enough to ensure efficient crosslinking of the basecoat at temperatures below 120 ° C.
  • Another disadvantage of the low molecular weight crosslinker molecules is that they have a low functionality and / or are hydrophilically modified, as a result of which the coating layers crosslinked therewith have poor weathering or chemical resistances.
  • a general way to achieve rapid crosslinking of a low-temperature curing varnish system is to increase the speed of the crosslinking reaction through the use of catalysts.
  • improvements in the crosslinking rate through the use of catalysts unfortunately go hand in hand with an unacceptable deterioration in the appearance of the coating since the crosslinking reaction of the catalyzed coating system already takes place during the course and film formation phase. This provides an irregular surface of the cured lacquer layer.
  • the course of the crosslinking reaction of the catalyzed coating system during the leveling and filming phase can be minimized in part by careful adjustment of the catalyst concentration.
  • Organozmnkatalysatoren such as Dialkylzinndialkoxide and - dialkanoate, especially dibutyltin dilaurate, used in paint systems.
  • organozmnkatalysatoren have the disadvantage that they have an unfavorable physiological profile and are thus criticized.
  • Derivatives of various metals, such as bismuth, zirconium, titanium or zinc, are therefore in the meantime also used as alternative catalysts, which, however, often have lower activities compared to the organozinc catalysts and / or are not so versatile.
  • this object is achieved by a method for producing a multilayer coating structure, which comprises the following steps: a) providing a substrate, b) applying at least one basecoat film, wherein the basecoat film is substantially free of melamine and its derivatives; c) applying at least one clear and / or topcoat layer comprising at least one polyisocyanate, at least one NCO-reactive compound and at least one thermolatent catalyst; d) Waiting for at least 30 seconds after step c) so that a film can form; e) curing of the multilayer coating structure with heat.
  • the multilayer paint structures produced by the process of the present invention using a thermolatent catalyst exhibit improved interlayer adhesion over the dibutyl tin dilaurate catalyzed systems known in the art.
  • the improved interlayer adhesion appears to be based on the fact that more time is available for the diffusion of the polyisocyanate into the basecoat by the thermolatent catalysis.
  • the inventive method thus allows a good crosslinking of the multilayer coating structure at low temperatures and short Ofenverweil Stammterrorism and can be advantageously used for the application of multilayer coating structures on temperature-sensitive substrates such as thermoplastics or composite materials that are not stable to deformation at elevated temperatures in an industrial manufacturing process become.
  • a further advantage of the method according to the invention is that the painting process, by means of which the significantly lower temperatures used in comparison with the conventional methods, is energy-efficient and inexpensive.
  • the invention furthermore relates to a multilayer paint system obtainable by the process according to the invention, to the use of the multilayer paint system for coating substrates, and to substrates which are coated with this multilayer paint system.
  • multi-layer coating structures are understood to mean those coating structures which comprise at least one basecoat film and at least one clearcoat and / or topcoat film.
  • Basecoat, topcoat and clearcoat can be of the same or different composition in their chemical composition.
  • the basecoat film, topcoat film and clearcoat film are preferably constructed differently in their chemical composition.
  • both the topcoat layer and the clearcoat layer comprise at least one NCO-reactive (isocyanate-reactive) compound.
  • NCO-reactive compound is understood as meaning a compound which can react with polyisocyanates to form polyisocyanate polyaddition compounds, in particular polyurethanes.
  • polyisocyanate compounds are compounds having at least two isocyanate groups per molecule.
  • NCO-reactive compounds it is possible to use all compounds known to the person skilled in the art which have an average OH or NH functionality of at least 1.5. These may be, for example, low molecular weight diols (eg 1,2-ethanediol, 1,3- or 1,2-propanediol, 1,4-butanediol), triols (eg glycerol, trimethylolpropane) and tetraols (eg pentaerythritol), short-term chain polyamines but also polyhydroxy compounds such as polyether polyols, polyester polyols, polyurethane polyols, polysiloxane polyols, polycarbonate polyols, polyether polyamines, polybutadiene polyols, polyacrylate polyols and / or polymethacrylate polyols and their copolymers, hereinafter called polyacrylate polyols.
  • diols eg 1,2-ethan
  • the polyhydroxy compounds preferably have mass-average molecular weights Mw> 500 daltons, measured by gel permeation chromatography (GPC) against a polystyrene standard, more preferably between 800 and 100,000 daltons, in particular between 1,000 and 50,000 daltons.
  • GPC gel permeation chromatography
  • the polyhydroxy compounds preferably have an OH number of 30 to 400 mg KOH / g, in particular between 100 and 300 KOH / g.
  • the hydroxyl number (OH number) indicates how much mg of potassium hydroxide is equivalent to the amount of acetic acid bound by 1 g of substance in the acetylation.
  • the sample is boiled in the determination with acetic anhydride-pyridine and the resulting acid is titrated with potassium hydroxide solution (DIN 53240-2).
  • the glass transition temperatures, measured by means of DSC measurements according to DIN-EN-ISO 1 1357-2, of the polyhydroxy compounds are preferably between -150 and 100 ° C., more preferably between -120 ° C. and 80 ° C.
  • Polyether polyols are accessible in a manner known per se by alkoxylation of suitable starter molecules with base catalysis or use of double metal cyanide compounds (DMC compounds).
  • Suitable starter molecules for the preparation of polyether polyols are, for example, simple, low molecular weight polyols, water, organic polyamines having at least two N-H bonds or any mixtures of such starter molecules.
  • Preferred starter molecules for the preparation of polyether polyols by alkoxylation, in particular by the DMC process are in particular simple polyols such as ethylene glycol, 1,3-propylene glycol and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 2-ethylhexanediol , 3, glycerol, trimethylolpropane, pentaerythritol and low molecular weight, hydroxyl-containing esters of such polyols with dicarboxylic acids of the type exemplified below or low molecular weight ethoxylation or propoxylation of such simple polyols or any mixtures of such modified or unmodified alcohols.
  • Alkylene oxides which are suitable for the alkoxylation are, in particular, ethylene oxide and / or propylene oxide, which can be used in any order or also in a mixture in the alkoxylation.
  • Polyester polyols are described, for example, in EP-A-0 994 1 17 and EP-A-1 273 640.
  • Polyester polyols can be prepared in a known manner by polycondensation of low molecular weight polycarboxylic acid derivatives, such as, for example, succinic acid, adipic acid, Suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetra- hydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimer fatty acid, trimer acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, citric acid or trimellitic acid, with low molecular weight polyols, such as ethylene glycol, Diethylene glycol, n
  • polyester polyols such as, for example, lactic acid, cinnamic acid or ⁇ -hydroxycaproic acid can also be polycondensed to form polyester polyols.
  • polyester polyols of oleochemical origin Such polyester polyols, for example, by complete ring opening of epoxidized triglycerides of an at least partially olefinically unsaturated fatty acid-containing fat mixture with one or more alcohols having 1 to 12 carbon atoms and by subsequent partial transesterification of the triglyceride derivatives to alkyl ester polyols having 1 to 12 carbon atoms in Alkyl residue can be produced.
  • Polyurethane polyols are preferably prepared by reacting polyester polyol prepolymers with suitable di- or polyisocyanates and are described, for example, in EP-A-1 273 640.
  • Suitable polysiloxane polyols are described, for example, in WO-A-01/09260, where the polysiloxane polyols cited therein can preferably be used in combination with other polyhydroxy compounds, in particular those having relatively high glass transition temperatures.
  • the polyacrylate polyols very particularly preferred according to the invention are generally copolymers and preferably have mass-average molecular weights Mw between 1,000 and 20,000 daltons, in particular between 1,500 and 10,000 daltons, in each case measured by gel permeation chromatography (GPC) against a polystyrene standard.
  • the glass transition temperature of the copolymers is generally between -100 and 100 ° C, in particular between -50 and 80 ° C (measured by DSC measurements according to DIN-EN-ISO 1 1357-2).
  • the polyacrylate polyols preferably have an OH number of 60 to 250 mg KOH / g, in particular between 70 and 200 KOH / g, and an acid number between 0 and 30 mg KOH / g.
  • the acid number here indicates the number of mg of potassium hydroxide which is consumed to neutralize 1 g of the respective compound (DIN EN ISO 21 14).
  • the preparation of suitable polyacrylate polyols is known per se to the person skilled in the art.
  • olefinically unsaturated monomers They are prepared by free-radical polymerization of hydroxyl-containing, olefinically unsaturated monomers or by free-radical copolymerization of hydroxyl-containing, olefinically unsaturated monomers with optionally other olefinically unsaturated monomers, such as ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, Butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, amyl acrylate, amyl methacrylate, hexyl acrylate, hexyl methacrylate, ethylhexyl acrylate, ethylhexyl me
  • Suitable hydroxyl-containing, olefinically unsaturated monomers are, in particular, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate and in particular 4-hydroxybutyl acrylate and / or 4- hydroxybutyl.
  • vinylaromatic hydrocarbons such as vinyltoluene, alpha-methylstyrene or, in particular, styrene, amides or nitriles of acrylic or methacrylic acid, vinyl esters or vinyl ethers, and in minor amounts, in particular, acrylic and / or methacrylic acid.
  • the clear and / or topcoat layer contains as NCO-reactive compound a polyhydroxy compound.
  • the polyhydroxy compound is selected from the group consisting of polyester polyols, polyurethane polyols, polysiloxane polyols, polycarbonate polyols, polyacrylate polyols and mixtures thereof.
  • the basecoat film is built up from known basecoat formulations which can be used both solventborne and aqueous.
  • the basecoat film is substantially free of melamine and its derivatives.
  • melamine and its derivatives in the basecoat film in amounts of less than 5 wt .-%, preferably less than 3 wt .-%, more preferably less than 1 wt .-%, based on the Total weight of the non-volatile components of the basecoat layer, are present.
  • Melamine or its derivatives present in these amounts in the basecoat film do not substantially contribute to the crosslinking of the basecoat film during curing under heat in accordance with step e) of the process according to the invention.
  • the basecoat layer is free of melamine and its derivatives.
  • the basecoat film according to the invention comprises at least one NCO-reactive compound.
  • NCO-reactive compounds which are suitable for the basecoat film are polyether polyols, polycarbonate polyols, polyester polyols, polyacrylate polyols, polyurethane polyols, polyacrylate polyols, as already described above for the clearcoat film.
  • One or more selected from polyester polyols, polyacrylate polyols and / or polyurethane polyols is preferably used as the NCO-reactive compound in the basecoat film.
  • the basecoat film comprises at least one NCO-reactive compound.
  • the basecoat is a Einkomponentenlack and has no pot life.
  • No pot life in this context means that the ready-to-apply basecoat is stable for more than 7 days, preferably more than 2 weeks, more preferably more than 4 weeks, ie also after 7 days, 2 weeks or 4 weeks with the same properties, as freshly prepared, can be used.
  • the clear and / or topcoat layer to be applied according to the invention in step c) comprises at least one polyisocyanate.
  • polyisocyanate in principle all polyisocyanates known to the person skilled in the art for the preparation of polyisocyanate polyaddition products, in particular polyurethanes, may be used, in particular the group of organic aliphatic, Cycloaliphatic, araliphatic and / or aromatic polyisocyanates having at least two isocyanate groups per molecule and mixtures thereof.
  • polyisocyanates examples include di- or triisocyanates, such as 1, 4-butane diisocyanate, 1,5-pentane diisocyanate (pentamethylene diisocyanate, PDI), 1, 6-hexane diisocyanate (hexamethylene diisocyanate, HDI), 4-isocyanatomethyl-l, 8-octane diisocyanate ( Triisocyanatononane, TIN), 4,4'-methylenebis (cyclohexylisocyanate) (H 12 MDI), 3,5,5-trimethyl-1-isocyanato-3-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1,3- and 1, 4-bis (isocyanatomethyl) cyclohexane (HeXDI), 1,5-naphthalene diisocyanate, diisocyanatodiphenylmethane (2,2'-, 2,4'- and 4,4'-MD
  • the clearcoat and / or topcoat layer contains as polyisocyanate an aliphatic and / or cycloaliphatic polyisocyanate.
  • the clearcoat and / or topcoat layer contains as polyisocyanate a derivative of hexamethylene diisocyanate and / or of pentamethylene diisocyanate, in particular a hexamethylene diisocyanate trimer and / or a pentamethylene diisocyanate trimer.
  • the ratio of polyisocyanates to NCO-reactive compounds in the clearcoat or topcoat layer is from 0.8 to 1.0 to 2.0 to 1.0, based on the molar amounts of the polyisocyanate groups to the NCO-reactive groups.
  • Preferred is a ratio of 1.0 to 1.0 to 1.5 to 1.0.
  • Particularly preferred is a ratio of 1.05 to 1.0 to 1.25 to 1.0.
  • both the basecoat film and the clearcoat and / or topcoat film may contain conventional auxiliaries and additives in effective amounts.
  • Effective amounts of solvent are preferably up to 150 wt .-%, more preferably up to 100 wt .-% and in particular up to 70 wt .-%, each based on the nonvolatile constituents of the respective coating agent (basecoat, topcoat or clearcoat ).
  • Effective amounts of other additives are preferably up to 25 wt .-%, more preferably up to 10 wt .-% and in particular up to 5 wt .-%, each based on the nonvolatile constituents of the respective coating agent (basecoat, topcoat or clearcoat).
  • auxiliaries and additives are, in particular, light stabilizers such as UV absorbers and sterically hindered amines (HALS), furthermore stabilizers, fillers and antisettling agents, antifoaming agents, anticrater agents and / or wetting agents, leveling agents, film-forming auxiliaries, reactive thinners, solvents, substances for Rheology control, slip additives and / or components that prevent soiling and / or improve the cleanability of the cured coatings, also matting agents.
  • light stabilizers such as UV absorbers and sterically hindered amines (HALS)
  • HALS sterically hindered amines
  • fillers and antisettling agents fillers and antisettling agents
  • antifoaming agents anticrater agents and / or wetting agents
  • leveling agents film-forming auxiliaries
  • reactive thinners reactive thinners
  • solvents substances for Rheology control
  • slip additives and / or components that prevent soiling and / or improve the cleanability of the cured coatings, also ma
  • light stabilizers in particular UV absorbers such as substituted benzotriazoles, S-phenyltriazines or oxalanilides and sterically hindered amines in particular with 2,2,6,6-tetramethyl-piperidyl structures - referred to as HALS - is described by way of example in A. Valet , Light stabilizer for paints, Vincentz Verlag, Hannover, 1996.
  • Stabilizers such as radical scavengers and other polymerization inhibitors such as hindered phenols stabilize paint components during storage and are intended to prevent discoloration during curing.
  • isocyanate-containing components are acidic stabilizers such as alkyl-substituted phosphoric acid esters and water scavengers such as triethyl ortho formate.
  • Preferred fillers are those compounds which do not adversely affect the appearance of the clearcoat or topcoat. Examples are nanoparticles based on silicon dioxide, aluminum oxide or zirconium oxide; in addition, reference is still made to the Römpp Lexikon »Paints and Printing Inks « Georg Thieme Verlag, Stuttgart, 1998, pages 250 to 252, referenced. If fillers, matting agents or pigments are in the clearcoat or topcoat, the addition of anti-settling agent may be useful to prevent separation of the ingredients during storage.
  • Wetting and leveling agents improve the surface wetting and / or the course of paints.
  • fluorosurfactants silicone surfactants and special polyacrylates.
  • Rheology controlling additives are important in order to control the properties of the liquid paint during application and in the course of the development on the substrate and are described, for example, in patents WO 94/22968, EP-A-0 276 501, EP-A-0 249 201 or WO 97/12945 known additives; crosslinked polymeric microparticles such as disclosed in EP-A-0081227; inorganic phyllosilicates such as aluminum magnesium silicates, sodium magnesium and sodium magnesium fluorine lithium phyllosilicates of the montmorillonite type; Silicas such as Aerosil®; or synthetic polymers having ionic and / or associative groups such as polyvinyl alcohol, poly (meth) acrylamide, poly (meth) acrylic acid, polyvinylpyrrolidone, styrene-maleic
  • Suitable solvents are used in a manner known to those skilled in the art, tailored to the binders used and the method of application. Solvents should dissolve the components used and promote their mixing and avoid incompatibilities. Furthermore, during the application and the curing, they should leave the coating coordinated with the ongoing crosslinking reaction, so that a solvent-free lacquer layer with the best possible appearance and without defects, such as a cooker or pinholes, is produced. In particular, solvents come into consideration, which are used in the technology of 2-component polyurethane clearcoats or topcoats.
  • ketones such as acetone, methyl ethyl ketone or hexanone
  • esters such as ethyl acetate, butyl acetate, methoxyproyl acetate, substituted glycols and other ethers, aromatics such as xylene or solvent naphtha from Exxon Chemie and mixtures of the solvents mentioned.
  • the topcoat layer and the basecoat may furthermore contain pigments, dyes and / or fillers.
  • the pigments used for this purpose including metallic or other effect pigments, dyes and / or fillers, are known to the person skilled in the art.
  • the clear and / or topcoat layer to be applied in step c) of the process according to the invention contains at least one thermolatent catalyst.
  • a thermolatent catalyst as used herein, is understood in particular to mean any catalyst which initiates the crosslinking reaction of the at least one polyisocyanate with the at least one NCO-reactive compound to form a urethane bond below 25 ° C., in particular below 30 ° C., preferably below 40 ° C.
  • thermolatent catalysts are inorganic tin-containing compounds which have no direct tin-carbon bond. It has proved to be particularly advantageous in the context of the invention if the thermolatent catalyst used in the clear and / or topcoat layer comprises cyclic tin compounds of the formula I, II or III or mixtures thereof: where:
  • D is -O-, -S- or -N (R1) - wherein Rl is a saturated or unsaturated, linear or branched, aliphatic or cycloaliphatic or an optionally substituted, aromatic or araliphatic radical having up to 20 carbon atoms, optionally Heteroatoms from the series oxygen, sulfur, nitrogen may contain, or for hydrogen or the rest
  • X, Y and Z are identical or different radicals selected from alkylene radicals of the formulas -C (R2) (R3) -, -C (R2) (R3) -C (R4) (R5) - or -C (R2) ( R3) -C (R4) (R5) -C (R6) (R7) - or ortho-arylene radicals of the formulas or wherein R 2 to R 1 independently of one another are saturated or unsaturated, linear or branched, aliphatic or cycloaliphatic or optionally substituted, aromatic or araliphatic radicals having up to 20 carbon atoms, which may optionally contain heteroatoms from the series oxygen, sulfur, nitrogen, or represent hydrogen;
  • D is -N (R1) -.
  • R 1 is preferably hydrogen or an alkyl, aralkyl, alkaryl or aryl radical having up to 20 C atoms or the radical particularly preferably hydrogen or an alkyl, aralkyl, alkaryl or aryl radical having up to 12 C atoms or the radical very particularly preferably hydrogen or a methyl, ethyl, propyl, butyl, hexyl or octyl radical, where propyl, butyl, hexyl, and octyl for all isomeric propyl,
  • Butyl, hexyl and octyl radicals are to Ph-, CH3PI1- or the rest
  • D * is -O-.
  • X, Y and Z are the te -C (R2) (R3), -C (R2) (R3) -C (R4) (R5) - or the ortho-arylene radical
  • R 2 to R 7 are preferably hydrogen or alkyl, aralkyl, alkaryl or aryl radicals having up to 20 C atoms, more preferably hydrogen or alkyl, aralkyl, alkaryl or aryl radicals having up to 8 C atoms. Atoms, most preferably hydrogen or alkyl radicals having up to 8 carbon atoms, even more preferably hydrogen or methyl.
  • R 8 to R 11 are preferably hydrogen or alkyl radicals having up to 8 carbon atoms, more preferably hydrogen or methyl.
  • R 12 is preferably hydrogen or an alkyl, aralkyl, alkaryl or aryl radical having up to 20 C atoms, more preferably hydrogen or an alkyl, aralkyl, alkaryl or aryl radical having up to 12 C atoms.
  • Atoms most preferably hydrogen or a methyl, ethyl, propyl, butyl, hexyl or octyl radical, wherein propyl, butyl, hexyl, and octyl for all isomeric propyl, butyl, hexyl - As well as octyl radicals.
  • L3 and L4 are Cl, MeO, EtO, PrO, BuO, HexO, OctO, PhO, formate, acetate, propanoate, butanoate, pentanoate, hexanoate, octanoate, laurate, Lactate or benzoate, wherein Pr, Bu, Hex and Oct represent all isomeric propyl, butyl, hexyl and octyl radicals, even more preferably Cl, MeO, EtO, PrO, BuO, HexO, OctO -, PhO-, hexanoate, laurate, or benzoate, wherein Pr, Bu, Hex and Oct stand for all isomeric propyl, butyl, hexyl and octyl radicals.
  • R15 to R20 are preferably hydrogen or alkyl, aralkyl, alkaryl or aryl radicals having up to 20 carbon atoms, more preferably hydrogen or alkyl, aralkyl, alkaryl or aryl radicals having up to 12 carbon atoms , very particularly preferably hydrogen, methyl, ethyl, propyl, butyl, hexyl or octyl radicals, where propyl, butyl, hexyl and octyl are suitable for all isomeric propyl, butyl, hexyl and octyl radicals.
  • PrN [CH 2 CH (Me) O-] 2 PrN [CH 2 CH (Me) O -] [CH (Me) CH 2 O-]
  • PrN [CH 2 C (Me) 2 O-] 2 PrN [CH 2 C (Me) 2 O -] [C (Me) 2 CH 2 O-]
  • BuN [ CH 2 CH (Me) O-] 2 BuN [CH 2 CH (Me) O -] [CH (Me) CH 2 O-] 2
  • BuN [CH 2 C (Me) 2 O-] 2 BuN [CH 2 C (Me) 2 O-] [C (Me) 2 CH 2 O-]
  • thermolatent catalysts suitable according to the invention are described, for example, in: EP 2 900 716 A1, EP 2 900 717 A1, EP 2 772 496 A1, EP 14182806, J.
  • tin compounds tend to oligomerize, so that polynuclear tin compounds or mixtures of mononuclear and polynuclear tin compounds are frequently present.
  • the tin atoms are preferably linked to one another via oxygen atoms ('oxygen bridges').
  • oxygen atoms 'oxygen bridges'.
  • Typical oligomeric complexes arise, e.g. by condensation of the tin atoms over oxygen or sulfur, e.g.
  • thermolatent catalyst is selected from the group of mono- or polycyclic tin compounds of the type: 1,1-di- "R” -5- "organyl” -5-aza-2,8-dioxa-1-stanna -cyclooctanes,
  • thermolatent catalyst is selected from:
  • thermolatent catalysts may be further known in the art
  • Catalysts / activators are combined; For example, titanium, zirconium, bismuth, tin (II) - and / or iron-containing catalysts, as described for example in WO 2005/058996. It is also possible to add amines or amidines. In addition, in the polyisocyanate polyaddition reaction, acidic compounds, e.g. 2-ethylhexanoic acid or alcohols may be added for reaction control.
  • Substrates suitable for the method according to the invention are, for example, substrates comprising one or more materials, in particular so-called composite materials.
  • a substrate which is composed of at least two materials is referred to as a composite material according to the invention.
  • Suitable materials include wood, metal, plastic, paper, leather, textiles, felt, glass, wood materials, cork, inorganic bonded substrates such as wood and fiber cement boards, electronic assemblies or mineral substrates.
  • Suitable composite types are, for example, particle composite materials, also referred to as dispersion materials, fiber composites, layered composites, also referred to as laminates, interpenetration composite materials and structural composite materials.
  • Suitable metals are, for example, steel, aluminum, magnesium and alloys of metals, as used in the applications of so-called wire, coil, can or container painting, and the like.
  • plastic also fiber-reinforced plastics, such as glass or carbon fiber reinforced plastics, and plastic blends of at least two or more plastics understood.
  • plastics which are suitable according to the invention are ABS, AMMA, ASA, CA, CAB, EP, UF, CF, MF, MPF, PF, PAN, PA, PE, HDPE, LDPE, LLDPE, UHMWPE, PET, PMMA, PP, PS, SB,
  • PUR, PVC, RF, SAN, PBT, PPE, POM, PUR-RIM, SMC, BMC, PP-EPDM and UP (abbreviated to DIN 7728T1). These can also be present in the form of films or as glass or carbon fiber reinforced plastics.
  • the substrates may be uncoated or coated.
  • primers and / or fillers may already have been applied to the substrate as a coating before it is used in the method according to the invention.
  • primers are, in particular, cathodic dipcoats used in automotive finishing, solvent-based or aqueous primers for plastics, in particular for plastics with low surface tension, such as PP or PP-EPDM.
  • the substrate to be provided according to the invention in step a) is a body or parts thereof which comprises one or more of the abovementioned materials.
  • the body or its parts comprises one or more materials selected from metal, plastic or mixtures thereof.
  • the substrate comprises metal, in particular, the substrate may be 80 wt .-%, 70 wt .-%, 60 wt .-%, 50 wt .-%, 25 wt .-%, 10 wt. -%, 5 wt .-%, 1 wt .-% consist of metal.
  • the substrate consists at least partially of a composite material, in particular of a composite material comprising metal and / or plastic.
  • the application of the at least one basecoat film and the at least one clearcoat and / or topcoat film to the substrate in steps b) and c) of the process according to the invention can be carried out in solution from solution, dispersion in a liquid dispersant such as water or from the melt, and powder coatings Form done.
  • a liquid dispersant such as water or from the melt, and powder coatings Form done.
  • the application is from solution.
  • Suitable methods of application are, for example, printing, brushing, rolling, casting, dipping, fluidized bed processes and / or preferably spraying such as compressed air spraying, airless spraying, high rotation, electrostatic spray application (ESTA), optionally combined with hot spray application such as hot air hot spraying ,
  • the number of basecoat films to be applied in step b) and clear and / or topcoat films in step c) is not limited to one layer. Consequently, in step b) it is also possible to apply two, three, four or more basecoat films. It is also possible within the scope of the invention in step c) of the method according to the invention to apply two, three, four or more clear and / or topcoat layers.
  • the NCO-reactive compound and / or the polyisocyanate may be present in a suitable solvent.
  • suitable solvents are those which have a sufficient solubility of the NCO-reactive compound and / or the polyisocyanate and are free of isocyanate-reactive groups.
  • solvents examples include acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, methyl isoamyl ketone, diisobutyl ketone, ethyl acetate, n-butyl acetate, ethylene glycol diacetate, butyrolactone, diethyl carbonate, propylene carbonate, ethylene carbonate, N, N-dimethylformamide, N, N-dimethylacetamide, N Methylpyrrolidone, N-ethylpyrrolidone, methylal, ethylal, butylal, 1,3-dioxolane, glycerolformal, benzene, toluene, n-hexane, cyclohexane, solvent naphtha, 2-methoxypropylacetate (MPA).
  • MPA 2-methoxypropylacetate
  • the NCO-reactive compound in step b) may also be present in solvents which carry isocyanate-reactive groups.
  • reactive solvents are those which have an average functionality towards isocyanate-reactive groups of at least 1.8.
  • These may be, for example, low molecular weight diols (for example 1,2-ethanediol, 1,3- or 1,2-propanediol, 1,4-butanediol), triols (for example glycerol, trimethylolpropane), but also low molecular weight diamines, for example polyaspartic esters, be.
  • the orientation of the metallic effect pigments can be disturbed by premixing of a clearcoat and therefore lead to a reduction in the flip-flop effect and / or to graying. If the drying or curing of the basecoat has progressed too far, the hardener may diffuse more poorly into the basecoat.
  • the clearcoat and / or topcoat to be applied in step c), comprising at least one polyisocyanate and at least one NCO-reactive compound, can be mixed both after mixing the clear and / or topcoat components are applied as well as only immediately mixed during the order.
  • the mixed clear and / or topcoat has a limited shelf life, the so-called pot life, since the crosslinking reaction is already progressing slowly after mixing.
  • the pot life is defined as the time in which the paint has doubled its viscosity (indirectly determined by doubling the flow time in the DIN cup, 4 mm).
  • the method according to the invention generally provides for the formation of a film.
  • coagulation and film formation of the clearcoat or topcoat applied to the substrate occur.
  • existing solvent and / or water slowly leaves the film by evaporation.
  • This process can be accelerated by supplying heat or air flow to the surface of the coating. It shrinks the film.
  • the crosslinking reaction of the at least one polyisocyanate with the at least one NCO-reactive compound of the clearcoat or topcoat material begins parallel to the evaporation of the solvent.
  • the heat or catalytically active paint constituents can accelerate the crosslinking reaction.
  • the crosslinking reaction does not take place during the film-forming phase, or only so slowly, that the polyisocyanates do not crosslink or do not significantly crosslink, so that they are able to diffuse into the basecoat. It may take 30 seconds to 12 minutes in the process according to the invention until the film has formed in step d) and any solvents and / or water which may have been present have substantially left the film.
  • step d) of the process according to the invention is preferably completed after 1 to 5 minutes, particularly preferably after 2 to 3 minutes.
  • step d) wait for at least 30, 45, 60, 120, 180 or 300 seconds, so that a film has been able to form before curing in step e).
  • the curing in step e) takes place at a substrate temperature of below 120 ° C., preferably below 110 ° C., more preferably below 100 ° C., in particular below 90 ° C.
  • the curing in step e) of the method according to the invention is advantageously substantially completed in less than 45 minutes.
  • the curing in step e) is substantially complete in less than 40 minutes, more preferably less than 35 minutes, most preferably less than 30 minutes.
  • Substantially complete as used herein means that the residual isocyanate content after curing in step e) is less than 20%, preferably less than 15%, more preferably less than 10%, more preferably less than 5%, most preferably less than 3%, based on the isocyanate content of the polyisocyanate in step c).
  • the percentage of isocyanate groups still present can be determined by comparing the content of isocyanate groups in% by weight in step c) with the content of isocyanate groups in% by weight after curing in step e), for example by comparing the intensity of the isocyanate band at about 2270 cm 1 by means of IR spectroscopy.
  • a further step f) can follow step e), in which the multilayer coating structure is detached again from the substrate in order to produce a film.
  • the invention furthermore relates to a multilayer paint system obtainable by the process according to the invention. It has been found, in particular, that the multilayer coating structures produced by the process according to the invention using a thermolatent catalyst differ materially and physically from the dibutyltin dilaurate-catalyzed systems known from the prior art. In particular, they have an improved intercoat adhesion.
  • Another object of the invention is the use of the obtainable by the process according to the invention multilayer paint system for coating substrates as well as substrates obtainable thereby, which are coated with the multilayer paint system according to the invention.
  • the substrate coated with the multilayer paint system according to the invention is a body, in particular a vehicle.
  • the vehicle may be constructed of one or more materials. Suitable materials are, for example, metal, plastic or mixtures thereof.
  • the vehicle may be any vehicle known to those skilled in the art.
  • the vehicle may be a motor vehicle, truck, motorcycle, scooter, bicycle or the like.
  • the vehicle is a motor vehicle and / or truck, more preferably it is a motor vehicle.
  • the substrate coated with the multilayer paint system according to the invention is a body or parts thereof which comprises one or more of the materials selected from metal, plastic or mixtures thereof. The invention will be explained in more detail by way of examples.
  • Bayhydrol A 2542 OH-containing acrylate polyol (Covestro, DE), DMEA: N, N-dimethylethanolamine, neutralizing agent (Aldrich, DE), 2-ethyl-1-hexanol: CAS 104-76-7, Colinater (Aldrich, Byk 347: Silicone surfactant for improving substrate wetting (Byk Chemie GmbH, DE), Byk 345: Silicone surfactant for improving substrate wetting (Byk Chemie GmbH, DE), Byk 011: Defoamer (Byk Chemie GmbH, DE), Byketol AQ: Silicone-free surface additive for avoiding stoves and bubbles (Byk Chemie GmbH, DE), Solus 3050: thickener based on cellulose acetobutyrate (Eastman, US), Rheovis AS 1130: thickener, anionic polyacrylate copolymer, (BASF, DE), n-butanol: 1-butanol, CAS 71-36-3, Colinate
  • an aqueous basecoat, black, based on a secondary acrylate (OH-containing) was prepared.
  • the components were weighed in succession, mixed and, as indicated in the formulation, dispersed with a dissolver with dispersing disk.
  • Pigment paste, black consisting of: 6,20
  • the clearcoat test formulations were calculated so that the polyisocyanate is in excess of 10%.
  • the addition amount of the leveling agent was calculated on the solid resin content.
  • the amount of catalyst was calculated as "ppm of tin based on the solid resin content of the polyisocyanate.”
  • the coating compositions were prepared by mixing the binders with the additives and stirring them at room temperature. Solventnaphta light (1: 1) used. The solvent amounts were chosen so that the theoretical solids content was the same.
  • the basecoat was applied to a PP plate by means of 50 ⁇ ⁇ and incubated for 20 min. dried at 80 ° C in a circulating air paint drying oven. Immediately after cooling (20 min RT), the clearcoat to be tested was then applied by spray application to the basecoat, flashed for 5 minutes at room temperature to allow film formation and then baked for 30 min at 100 ° C in a circulating air paint drying oven.
  • the layer thicknesses of the basecoat and of the clearcoat are identical in all experimental setups (layer thickness basecoat: 12-14 ⁇ m, layer thickness clearcoat: about 40 ⁇ m).
  • the lacquer structure was removed from the PP plate and then the base lacquer on the underside was measured by means of an FT-IR spectrometer (Tensor II with Platinum ATR unit (diamond crystal) from Bruker). Triplicate measurements were carried out.
  • thermolatent catalyst allows for greater migration of isocyanate throughout the basecoat compared to DBTL, as evidenced by the larger peak area / absorbance units measured on the bottom of the basecoat.
  • the clearcoat test formulations were calculated so that the polyisocyanate is equimolar crosslinked with the polyol.
  • the addition amount of the leveling agent was calculated on the solid resin content.
  • the amount of catalyst was calculated as "ppm of tin based on the solid resin content of the polyisocyanate.”
  • the coating compositions were prepared by mixing the binders with the additives and stirring them at room temperature. Methoxypropylacetate-2 / Solventnaphta light (1: 1) used. The amounts of solvent were chosen so that the theoretical solids contents were the same.
  • thermolatent catalyst thermolatent catalyst
  • DBTL dibutyltindilaurate
  • intensity of the NCO peak at wavenumber 2274 cm 4
  • the results (relative change in the intensity of the NCO peaks in%>) are shown in the following table:
  • Pigment paste, black consisting of: 5,50
  • the clearcoat coupons were calculated so that the polyol is in excess of 10%.
  • the addition amount of the leveling agent was calculated on the solid resin content.
  • the amount of catalyst was calculated as "ppm of tin based on the solid resin content of the polyisocyanate.”
  • the coating compositions were prepared by mixing the binders with the additives and stirring them at room temperature. ventnaphta light (1: 1) used. The amounts of solvent were chosen so that the solids were the same.
  • thermolatent catalyst thermolatent catalyst
  • DBTL dibutyltindilaurate
  • the basecoat was coated on a Bayblend T85 XF plate by means of a 50 ⁇ spiral doctor blade and incubated for 10 min. dried at 80 ° C in a circulating air paint drying oven.
  • the clear coat to be tested was then applied by means of 50 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ , applied to the basecoat, flashed for 10 minutes at room temperature and then baked for 30 min at 100 ° C in a circulating air paint drying oven .
  • the plate material was aged for 16 hours at 60 ° C.
  • the layer thicknesses of the basecoat and of the clearcoat materials are identical in all experimental setups (layer thicknesses of the basecoats: 12 ⁇ mol-13 ⁇ m, layer thicknesses of the clearcoat materials: 30-34 ⁇ mol).
  • the coated plate material was stored for 1 h in 95 ° C to 98 ° C hot water and then regenerated for 4 hours at atmospheric conditions. Then the adhesion was tested by cross-hatching with a multi-blade knife according to DIN EN ISO 2109 (blade spacing 1 mm and 2 mm). Loose particles were removed with 3M brand "Scotch Pressure Sensitive Tape", which was rubbed onto the cutting grid with a thumbnail and jerkily pulled off the coating as vertically as possible. The damage picture was graded with a magnifying glass and evaluated on the basis of the sectional images shown in the DIN standard. GT 0 means that the sectional images are completely smooth and that no parts have flaked off.
  • the so-called coin test was carried out elsewhere.
  • the paint was scratched down to the plastic substrate with a coin with a sharp edge and then the exposed surfaces were assessed with a magnifying glass.
  • the force is to be chosen so that the coin penetrates into the paint down to the ground, so that after removing the coin in any case, the substrate is visible.
  • thermolatent catalyst thermolatent catalyst
  • DBTL dibutyltindilaurate

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Abstract

La présente invention concerne un procédé pour la production d'une structure de laque multicouche, qui présente les étapes suivantes : a) mise à disposition d'un substrat ; b) application d'au moins une couche de laque de base, la couche de laque de base étant essentiellement exempte de mélamine et de ses dérivés ; c) application d'au moins une couche de laque claire et/ou de recouvrement, comprenant au moins un polyisocyanate, au moins un composé réactif avec NCO et au moins un catalyseur thermolatent ; d) attente d'au moins 30 secondes après l'étape c) de telle sorte qu'un film peut se former ; et e) durcissement de la structure de laque multicouche avec apport de chaleur. L'invention concerne également la structure de laque multicouche pouvant être obtenue par le procédé selon l'invention, l'utilisation de la structure de laque multicouche pour le revêtement de substrats ainsi que des substrats revêtus par la structure de laque multicouche.
PCT/EP2016/078160 2015-11-20 2016-11-18 Structure de laque multicouche présentant un catalyseur thermolatent WO2017085268A1 (fr)

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US15/776,109 US20180320019A1 (en) 2015-11-20 2016-11-18 Multi-layer coating structure having a thermally latent catalyst
CN201680079625.9A CN108472684B (zh) 2015-11-20 2016-11-18 具有热潜伏性催化剂的多层漆结构
EP16802006.3A EP3377235A1 (fr) 2015-11-20 2016-11-18 Structure de laque multicouche présentant un catalyseur thermolatent

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